Metal complexes of azomethines

ABSTRACT

Metal complexes of azomethines of the formula ##STR1## are useful for coloring plastics and lacquers in yellow to red shades of excellent fastness properties.

This is a divisional of application Ser. No. 773,990, filed on Mar. 3,1977, now U.S. Pat. No. 4,132,708, issued Jan. 2, 1979; which is adivisional of application Ser. No. 545,457, filed on Jan. 30, 1975, nowU.S. Pat. No. 4,022,770, issued May 10, 1977.

The invention provides novel, useful metal complexes of azomethines anda process for their manufacture which comprises treating an azomethineof the formula ##STR2## wherein R₁ represents a hydrogen atom, an alkylor an aryl group, R₂ represents an isocyclic or a heterocyclic radicalwith a hydroxy group adjacent to the azomethine group, or R₁ and R₂together with the carbon atom of the azomethine group represent a 5- or6-membered heterocyclic ring which may be fused with benzene nuclei,each of X₁ and X₂ independently represents alkyl, cycloalkyl, aralkyl oraryl radicals or together X₁ and X₂ represent a fused carbocyclic orheterocyclic aromatic ring and Y represents the radical of a compoundcontaining active methylene groups, of a heterocyclic amine or of ahydrazide, with an agent which denotes bivalent metal.

In formula (I) as well as in the formulae listed hereinafter, referenceis made to only one of all possible tautomeric or mesomeric structures.

Preferably, there are used as starting compounds azomethines of theformula ##STR3## wherein R₁, R₂ and Y have the meanings already assignedto them, Hal represents a halogen atom, Y₅ represents an oxygen or asulphur atom, R₅ represents an unsubstituted or a substituted alkyl,cycloalkyl or aryl group, Z represents a hydrogen atom, m, n and p areintegers from 0 to 4 and the sum of m+n+p is 4.

Compounds of especial interest are azomethine metal complexes of theformula ##STR4## and, in particular, those of the formula III wherein Yrepresents the radical of a compound containing active methylene groupsand especially the radical of the formula ##STR5## In the formulae (III)and (IV), A represents an isocyclic or a heterocyclic radical, R₃represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, M₁represents a Ni, Cu, Co or Zn atom and a cyano group, R₄ represents anacyl, an alkoxycarbonyl, a carbamoyl or a sulphamoyl group or a radicalof the formula ##STR6## wherein V represents an oxygen or a sulphur atomor an imino group, Y₂ and Y₃ represent hydrogen or halogen atoms, alkylor alkoxy groups of 1 to 4 carbon atoms or nitro groups.

Particularly preferred azomethine complexes are those of the formula##STR7## wherein R₃, R₄, M₁, Y₂ and Y₃ have the meanings alreadyassigned to them and Y₄ represents an oxygen or a sulphur atom or a NHgroup.

Preferred metal complexes of azomethines are also those of the formula##STR8## wherein Y has the meaning previously assigned to it, Z₁ and Z₃represent hydrogen or halogen atoms, alkoxy or alkylmercapto groups of 1to 6 carbon atoms, cycloalkyl groups of 5 to 6 carbon atoms, aralkoxy,aryloxy or arylmercapto groups, Z₂ and Z₄ represent hydrogen or halogenatoms, and one of the substituents Z₁ to Z₄ can also be a nitro group,and, in particular, those wherein Y represents a radical of the formula##STR9## in which R₄ has the meaning previously assigned to it.

Preferred metal complexes of azomethines are also those of the formulaeII and III wherein Y represents a radical of the formulae ##STR10##wherein Y₂, Y₃ and Y₄ have the meanings previously assigned to them andR₆ represents a hydrogen atom or an alkyl group of 1 to 4 carbon atomsor a phenyl radical which is unsubstituted or a phenyl radical which issubstituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbonatoms.

The azomethines used as starting materials (ligands) are in part knowncompounds. They are obtained by known processes, for example by

(a) condensation of a compound of the formula ##STR11## with a hydrazoneof the formula ##STR12## or by

(b) condensation of a compound of the formula ##STR13## with a compoundof the formula H₂ Y, in which formulae X₁, X₂, R₁, R₂ and Y have themeanings previously assigned to them, or by

(c) condensation of a hydrazone of the formula ##STR14## with an oxocompound of the formula ##STR15## or the anil thereof of the formula##STR16## wherein Ph represents an unsubstituted or substituted phenylradical.

The compounds of the formula (VI) are obtained by condensation of anamino-imine of the formula ##STR17## with a heterocyclic primary amine,a compound containing active methylene groups or with a hydrazide.

The compounds of the formula (VIII) are obtained by condensation of anamino-imine of the formula (IX) with a hydrazone of the formula (VII).

The compounds of the formula (VIIIa) are obtained by condensation of thecompound of the formula (VI) with hydrazine.

The manner in which the ligands are manufactured can exert a substantialinfluence on their physical and colouristic properties and on theirmetal complexes.

Examples of amino-imines of the formula (IX) are:

2-amino-3,4-dichloro-pyrrolenine

2-amino-5-imino-3,4-dimethyl-pyrrolenine

2-amino-5-imino-3,4-diethyl-pyrrolenine

2-amino-5-imino-3,4-dicyclohexyl-pyrrolenine or

2-amino-5-imino-3,4-diphenyl-pyrrolenine.

Particular interest, however, attaches to the1-amino-3-iminoisoindolenines of the formula ##STR18## wherein Hal, RY,Z, m, n and p have the meanings previously assigned to them.

As examples there may be mentioned principally the unsubstituted1-amino-3-imino-isoindolenine, also

4,5,6,7-tetrachloro-1-amino-3-imino-isoindolenine,

5,6-dichloro-1-amino-3-imino-isoindolenine,

4,5,7-trichloro-6-methoxy-1-amino-3-imino-isoindolenine

4,5,7-trichloro-6-ethoxy-1-amino-3-imino-isoindolenine

4,5,7-trichloro-6-phenoxy-1-amino-3-imino-isoindolenine

5,7-dichloro-4,6-dimethoxy-1-amino-3-imino-isoindolenine

5,7-dichloro-4,6-diphenoxy-1-amino-3-imino-isoindolenine

4,5,7-trichloro-6-methylmercapto-1-amino-3-imino-isoindolenine

4,5,7-trichloro-6-phenylmercapto-1-amino-3-imino-isoindolenine

1-amino-3-imino-4,5-benz-isoindolenine

4,5,6,7-tetraphenoxy-1-amino-3-imino-isoindolenine

5- or 6-methyl-1-amino-3-imino-isoindolenine

5- or 6-phenyl-1-amino-3-imino-isoindolenine

4- or 7-chloro-1-amino-3-imino-isoindolenine

5- or 6-chloro-1-amino-3-imino-isoindolenine

5,6-dichloro-1-amino-3-imino-isoindolenine

4- or 7-nitro-1-amino-3-imino-isoindolenine

5- or 6-nitro-1-amino-3-imino-isoindolenine

5- or 6-methoxy-1-amino-3-imino-isoindolenine

5- or 6-ethoxy-1-amino-3-imino-isoindolenine

5- or 6-phenoxy-1-amino-3-imino-isoindolenine

5- or 6-methylmercapto-1-amino-3-imino-isoindolenine

5- or 6-methylsulphonyl-1-amino-3-imino-isoindolenine

5- or 6-acetylamino-1-amino-3-imino-isoindolenine

As further amino-imino-isoindolenines there may be cited:

1-amino-3-imino-4,7-dithia-4,5,6,7-tetraydro-isoindolenine and1-amino-3-imino-4,7-diaza-isoindolenine.

The cited 1-amino-3-imino-indolenines can be obtained, for example, fromthe corresponding phthalonitriles by treatment with liquid ammonia orfrom the dicarboxylic imides via the 1,3,3-trichloro-isoindolenines,which are subsequently reacted with ammonia.

The phthalonitriles which contain alkoxy, phenoxy or alkylmercaptogroups can be obtained from the tetrachlorophthalonitrile by reactionwith an alkali alcoholate, phenolate or mercaptide in a hydrophilicorganic solvent.

The reaction of the cited 1-amino-3-iminoisoindolenines withheterocyclic amines to manufacture the compound of the formula (VI) iscarried out desirably in the molar ratio 1:1 in a polar organic solvent,preferably an alcohol, such as methanol, ethanol, isobutanol or methylcellosolve, at temperatures between 50° and 120° C.

The heterocyclic primary amines are preferably those in which theprimary amino group is located directly at a 5- or 6-memberedheterocyclic ring which can contain 3 nitrogen atoms and in additionoxygen and sulphur atoms. A benzene nucleus which may be substituted orunsubstituted can be fused to the heterocyclic parent nucleus. Asexamples there may be cited.

2-aminothiophene

2-aminothiazole

2-amino-5-nitrothiazole

2-amino-5-methylsulphonyl-thiazole

2-amino-5-cyanothiazole

2-amino-4-methyl-5-nitrothiazole

2-amino-4-methylthiazole

2-amino-4-phenylthiazole

2-amino-4-(4'-chloro)-phenylthiazole

2-amino-4-(4'-nitro)-phenylthiazole

3-aminopyrazole

3-amino-1-phenylpyrazole

3-aminoindazole

5-methylsulphonyl-2-aminothiazole

5-benzoyl-2-aminothiazole

2-aminoimidazole

4,5-dicyano-2-aminoimidazole

4,5-diphenyl-2-aminothiazole

2-amino-3,4-thiadiazole

2-amino-3,5-thiadiazole

3-amino-1,2,4-triazole

2-amino-3,4-oxadiazole

3-aminopyridine

2-aminopyridin-N-oxide

2-amino-benzthiazole

2-amino-6-chloro-benzthiazole

2-amino-6-methyl-benzthiazole

2-amino-6-methoxy-benzthiazole

2-amino-6-chloro-4-nitrobenzthiazole

2-amino-6-bromo-4-cyanobenzthiazole

2-amino-6-cyano-4-methylbenzthiazole

2-amino-6-methyl-4-nitrobenzthiazole

2-amino-6-methoxy-4-nitrobenzthiazole

2-amino-6-butoxy-4-chlorobenzthiazole

2-amino-4-chloro-5-methoxybenzthiazole

2-amino-4-bromo-6-methoxybenzthiazole

2-amino-4,6-dichlorobenzthiazole

2-amino-4,6-dibromobenzthiazole

2-amino-4-methyl-6-(trifluoromethyl)-benzthiazole

2-amino-4-methyl-6-propionylbenzthiazole

2-amino-4-chloro-6-(methylsulphonyl)-benzthiazole

3-aminobenzisothiazole

3-amino-5-chloro-benzisothiazole

2-amino-3-cyano-tetrahydrobenzthiophene

2-amino-benzimidazole

2-amino-6-chloro-benzimidazole

2-amino-6-bromo-benzimidazole

2-amino-6-methyl-benzimidazole

2-amino-6-methoxy-benzimidazole

2-amino-6-ethoxy-benzimidazole

2-amino-6-methylsulphonyl-benzimidazole

2-amino-6-acetylamino-benzimidazole

Instead of reacting the compounds of the formulae (VIII) or (IX) withamines, it is also possible to react them with compounds containingactive methylene groups.

The compounds containing active methylene groups can be classified asfollows:

(a) Substituted acetonitriles, in particular those of the

R₄ CH₂ CN,

wherein R₄ has the meaning already assigned to it.

Examples of simply substituted acetonitriles are:

malonitrile

cyanoacetic acid methyl, ethyl, propyl or butyl ester

cyanoacetamide

cyanoacetic acid methylamide or ethylamide

cyanoacetic acid phenylamide

α-cyano-dimethyl ketone

cyanomethyl ethyl ketone

α-cyanoacetophenone

phenylacetonitrile

phenylsulphonylacetonitrile

phenylsulphamoylacetonitrile

sulphamoyl.

Examples of heterocyclic substituted acetonitriles are:

2-cyanomethyl-oxazole

2-cyanomethyl-thiazole

2-cyanomethyl-imidazole

2-cyanomethyl-1,2,3-triazole

2-cyanomethyl-4-hydroxy-quinazoline

2-cyanomethyl-benzoxazole

2-cyanomethyl-benzthiazole

2-cyanomethyl-benzimidazole

2-cyanomethyl-5-chlorobenzimidazole

2-cyanomethyl-5-nitrobenzimidazole

2-cyanomethyl-5,6-dimethylimidazole

2-cyanomethyl-5-ethoxyimidazole

2-cyanomethyl-5,6-dichloroimidazole

2-cyanomethyl-5-methoxyimidazole

2-cyanomethyl-dihydro-quinazolone-4

and the compound of the formula ##STR19##

(b) Pyridines, quinolines, cumarins and pyrimidines, for example:

4-methyl-2,6-dioxo-tetrahydro-pyridine

4-methyl-5-cyano-2,6-dioxo-tetrahydro-pyridine

4-methyl-5-carbamoyl-2,6-dioxo-tetrahydro-pyridine

4-methoxycarbonyl-2,6-dioxo-tetrahydro-pyridine

1,4-dimethyl-2,6-dioxo-tetrahydro-pyridine

1-phenyl-4-methyl-2,6-dioxo-tetrahydro-pyridine

4,6-dioxo-tetrahydro-pyrimidine

1,3-dioxo-tetrahydro-isoquinoline

4-hydroxycumarin

(c) Barbituric acid and derivatives, for example:

barbituric acid

methyl-, ethyl- or phenylbarbituric acid

2-thiobarbituric acid

2-iminobarbituric acid

1-phenylbarbituric acid

1,3-dimethylbarbituric acid

1-methylbarbituric acid

(d) Pyrazolones, for example:

3-methyl-pyrazolone-5

1-phenyl-3-methyl-pyrazolone-5

3-methoxycarbonyl-pyrazolone-5

1-phenyl-3-carbamoyl-pyrazolone-5

(e) Imidazoles, oxazoles, isoxazoles and thiazoles, for example:

oxazolone-5

2-methyl-oxazolone-5

2-phenyl-oxazolone-5

isoxazolone-5

3-methyl-isoxazolone-5

3-phenyl-isoxazolone-5

imidazolidin-2,4-dione

3-methyl-benzthiazoline.

The condensation of the compounds of the formula (VIII) or (IX) with thecompounds containing active methylene groups is effected desirably attemperatures between 10° and 110° C. in an organic solvent, expedientlyin a hydrophilic organic solvent, especially in an aliphatic alcohol,for example methanol, propanols, butanols, glycols and glycol monoethersor in acetic acid, if appropriate in mixtures with water.

Instead of compounds containing active methylene groups, it is alsopossible to condense hydrazides, for example the hydrazides of aliphaticmonocarboxylic acids containing 2 to 4 carbon atoms or, in particular,the hydrazides of the formula ##STR20## wherein Y₂ and Y₃ have themeanings previously assigned to them, with the imines of the formulaeVIII or IX.

The condensation of the hydrazides with the compounds of the formulaeVIII or IX is desirably carried out in water or in an organic solvent atelevated temperature, preferably between 50° C. and the boiling point ofthe solvent employed. Examples of solvents are: water, alcohol, glacialacetic acid, dioxan, dimethyl formamide, N-methylpyrrolidone,butylrolacetone, glycol monomethyl ether, xylene, chlorobenzene,o-dichlorobenzene, nitrobenzene or mixtures thereof.

The reaction according to process (a) of the compounds of the formula(VI) with the hydrazones of the formula VII, preferably with those ofthe formula ##STR21## wherein A and R₃ have the indicated meanings, iscarried out at temperatures between 50° and 130° C. in an organicsolvent and diluent.

Suitable solvents and diluents are polar organic solvents, above allthose which are miscible with water, such as alcohols, N,N-dimethylformamide, N,N-diethyl formamide, N,N-diethyl acetamide, N,N-dimethylacetamide, N-methylpyrrolidone, glacial acetic acid, formic acid, glycolmonomethyl ether, glycol monoethyl ether or mixtures thereof.

The hydrazones, the majority of which are known compounds, are obtainedby reaction of the corresponding oxo compound of the formula ##STR22##or aldimines thereof of the formula ##STR23## wherein R₁ and R₂ have theindicated meanings and Ph represents an unsubstituted or a substitutedphenyl radical, in particular those of formula ##STR24## wherein R₃ andPh have the indicated meanings, by known processes with hydrazinehydrate.

The oxo compounds of the formula ##STR25## or the aldimines thereof canbelong to both the aromatic and the heterocyclic class.

Particularly interesting oxo compounds are those of the formula##STR26## wherein Y₂, Y₃ and Y₄ have the meanings already assigned tothem, R₇ represents a hydrogen atom or a methyl group, and especiallythe hydroxyquinolines or hydroxycumarins of the formulae ##STR27##wherein R₇, Y₂ and Y₃ have the indicated meanings.

Particular attaches also to the compounds of the following formulae##STR28## wherein R₇ has the meaing previously assigned to it, R₈represents a cyano, alkoxycarbonyl group or a carbamoyl group and R₉represents a hydrogen atom, an alkyl, aryl or a hydroxy group, ##STR29##wherein Y₂, Y₃, R₇ and R₈ have the meanings assigned to themhereinbefore, ##STR30## wherein Y₂, Y₃ and Y₇ have the meanings assignedto them hereinbefore, and also hydroxynaphthaldehydes of the formula##STR31## wherein Y₆ represents a hydrogen atom, a carboxy or acarbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2to 6 carbon atoms, an phenylcarbamoyl group which is unsubstituted orwhich is substituted in the phenyl moiety by halogen atoms or alkyl oralkoxy groups of 1 to 4 carbon atoms, Y₇ represents a hydrogen or ahalogen atom, a methoxy, nitro or cyano group, or pyrazoles of theformula ##STR32## wherein Y₂ and Y₃ have the indicated meanings, Qrepresents a methyl group or an alkoxycarbonyl group containing 2 to 5carbon atoms or a carbamoyl group.

The following aldehydes or ketones may be cited as examples:

(1.) o-hydroxybenzaldehydes:

salicylaldehyde

4-chloro-2-hydroxybenzaldehyde

5-chloro-2-hydroxybenzaldehyde

3-nitro-2-hydroxybenzaldehyde

5-nitro-2-hydroxybenzaldehyde

3,5-dichloro-2-hydroxybenzaldehyde

3,5-dibromo-2-hydroxybenzaldehyde

5-phenylazo-2-hydroxybenzaldehyde

5-(2'-chloro-phenylazo)-2-hydroxybenzaldehyde

5-(2',5'-dichloro-phenylazo)-2-hydroxybenzaldehyde

5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde

5-(2'-methoxy-phenylazo)-2-hydroxybenzaldehyde

5-(2'-methoxy-4'-nitro-phenylazo)-2-hydroxybenzaldehyde

5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde

(2.) Hydroxynaphthaldehydes:

2-hydroxynaphthaldehyde

6-bromo-2-hydroxynaphthaldehyde

5-nitro-2-hydroxynaphthaldehyde

2-hydroxy-3-carboxy-naphthaldehyde

2-hydroxy-3-methoxycarbonyl-naphthaldehyde

2-hydroxy-3-phenylcarbamoyl-naphthaldehyde

2-hydroxy-3-(4'-chlorophenylcarbamoyl)-naphthaldehyde

2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl-naphthaldehyde

2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenylcarbamoyl-naphthaldehyde

2-hydroxy-6-bromo-3-carboxynaphthaldehyde

2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.

(3.) Heterocyclic aldehydes and ketones:

2,6-dihydroxy-4-methyl-5-cyano-3-pyridinaldehyde

2,6-dihydroxy-4-methyl-5-carbamoyl-3-pyridinaldehyde

2,4-dihydroxy-3-quinoline aldehyde

5-chloro-2,4-dihydroxy-3-quinoline aldehyde

6-chloro-2,4-dihydroxy-3-quinoline aldehyde

7-chloro-2,4-dihydroxy-3-quinoline aldehyde

8-chloro-2,4-dihydroxy-3-quinoline aldehyde

6,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde

7,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde

6-methyl-2,4-dihydroxy-3-quinoline aldehyde

7-methyl-2,4-dihydroxy-3-quinoline aldehyde

8-methyl-2,4-dihydroxy-3-quinoline aldehyde

6-chloro-8-methyl-2,4-dihydroxy-3-quinoline aldehyde

2,4-dihydroxy-3-acetyl-quinoline

2,4-dihydroxy-3-acetyl-6-methyl-quinoline

2,4-dihydroxy-3-acetyl-6-chloro-quinoline

3-hydroxy-isoquinoline-4-aldehyde

5-formyl-bartituric acid

2-methyl-4,6-dihydroxy-5-pyrimidine aldehyde

2-phenyl-4,6-dihydroxy-5-pyrimidine aldehyde

4-hydroxy-3-quinaldine aldehyde

6-chloro-4-hydroxy-3-quinaldine aldehyde

6-methoxy-4-hydroxy-3-quinaldine aldehyde

4-hydroxycumarin-3-aldehyde

6-methyl-4-hydroxycumarin-3-aldehyde

6-methoxy-4-hydroxycumarin-3-aldehyde

6-chloro-4-hydroxycumarin-3-aldehyde

5,7-dimethyl-6-chloro-4-hydroxycumarin-3-aldehyde

1-phenyl-3-methyl-4-formyl-pyrazolone-5

1-phenyl-3-carboxy-4-formyl-pyrazolone-5

1-phenyl-3-methoxycarbonyl-4-formyl-pyrazolone-5

1-phenyl-3-ethoxycarbonyl-4-formyl-pyrazolone-5

1-(2'-chlorophenyl)-3-methyl-4-formyl-pyrazolone-5

1-(4'-chlorophenyl)-3-methyl-4-formyl-pyrazolone-5

1-(2'-methylphenyl)-3-methyl-4-formyl-pyrazolone-5

1-(4'-methylphenyl)-3-methyl-4-formyl-pyrazolone-5

1-phenyl-3-carbamoyl-4-formyl-pyrazolone-5

As hydrazones of the formula (VII) it is also possible to use those ofthe formula ##STR33## wherein Z₁ to Z₄ have the meanings previouslyassigned to them. These are obtained by reaction of hydrazine with anisoindolinone of the formula ##STR34## wherein Z₁ to Z₂ have themeanings previously assigned to them, V₁ represents a group of theformula ##STR35## wherein Z₈ represents an imino or a thio group andboth symbolds Z₉ represents halogen atoms, alkoxy or secondary aminogroups.

As starting materials there are preferably used 3-imino-isoindolinone or3,3'-dialkoxy-iminoisoindolinones of the formula ##STR36## wherein Z₁ toZ₄ have the meanings previously assigned to them and R' represents analkyl group of 1 to 4 carbon atoms. Those starting materials in which Z₁to Z₄ represent chloride atoms or hydrogen atoms are known, and those inwhich Z₁ and Z₃ represent alkoxy, cycloalkoxy, aralkoxy, aryloxy,alkylthio or arylthio groups and Z₂ and Z₄ represent chlorine atoms canbe obtained by reaction of an ammonium salt or ester oftetrachloro-o-cyanobenzoic acid in a hydrophilic organic solvent with acompound of the formula Z₁ M₃, wherein Z₁ has the meaning previouslyassigned to it and M₃ represents an alkali metal atom, and, ifnecessary, esterifying the resultant product.

Examples of isoindolinones are:

3,3-dimethoxy-4,5,6,7-tetrachloro-isoindolinone

3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone

3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone

3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone

3,3-dimethoxy-4,7-dichloro-isoindolinone

3,3-dimethoxy-4-nitro-isoindolinone

3,3-dimethoxy-5-nitro-isoindolinone

3,3-dimethoxy-4-fluoro-isoindolinone

3,3-dimethoxy-7-iodo-isoindolinone

3-imino-isoindolinone

5-chloro-3-imino-isoindolinone

5,6-dichloro-3-imino-isoindolinone

The ligands can also be manufactured by process modification (b), i.e.by condensation of a compound of the formula (VIII) with a compound ofthe formula H₂ Y.

It is preferred to use as starting material a compound of the formula##STR37## wherein the symbols have the meanings previously assigned tothem. As compounds of the formula H₂ Y it is desirable to use thecompounds containing active methylene groups, heterocyclic amines orhydrazides cited hereinbefore. The reaction is desirably carried out ina polar organic solvent at temperatures between 50° and 120° C.

Compounds of the formula ##STR38## wherein the symbols have the meaningspreviously assigned to them, are preferably used as starting materials.The aldehydes or ketones or anils thereof cited hereinbefore can bepreferably used as oxo compounds. The reaction is carried out preferablyat temperatures between 50° and 130° C. in the above mentioned organicsolvents and diluents.

Since the ligands are sparingly soluble as a rule in the solvents usedfor the reaction, it is possible to isolate them easily by filtration.Any impurities can be removed by washing off.

The ligands are converted into the metal complexes by treating them withagents which donate bivalent metals, for example with salts of zinc,dadmium, maganese, cobalt, iron, but especially of copper and nickel ormixtures of such metals. Preferably, the formiates, acetates orstearates of these metals are used. The metallising takes place, forexample, in water, if appropriate with the addition of a dispersant, butdesirably in one of the solvents cited hereinbefore.

A further embodiment of the process according to the invention consistsin

(a) condensing hydrazone of the formula VII with a compound of theformula VI (single step process I), or

(b) condensing a compound of the formula VIII with a compound of theformula H₂ Y, wherein Y has the indicated meaning (single step processII), or

(c) condensing a hydrazine of the formula VIIIa with an oxo compound ofthe formula ##STR39## or the anvil thereof (single step process III), inthe presence of an agent which donates a bivalent metal. These differentmetallising processes are able to result in metal complexes withdifferent physical and colouristic properties. In principle, each of thesingle step processes I, II and II yields the same metal complexes asthe metallising of the ligands obtained according to processes (a), (b)and (c).

The novel colourants constitute useful pigments which, in finely dividedform, may be used for pigmenting organic material of high molecularweight, for example cellulose ethers and esters, polyamides andpolyurethanes or polyesters, acetyl cellulose, nitrocellulose, naturalresins or synthetic resins, such as polymerisation or condensationresins, for example aminoplasts, in particular urea andmelamine/formaldehyde resins, alkyl resins, phenolic plastics,polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride,polyethylene, polypropylene, polyacrylonitrile, polyacrylic esters,rubber, casein, silicon and silicone resins, individually or inmixtures.

It is immaterial whether the cited materials of high molecular weightare in the form of plastics, melts or in the form of spinning solutions,lacquers or printing inks. Depending on the use to which they are put,it is advantageous to use the novel pigments as toners or in the form ofpreparations.

The resultant colourations are characterised by good general pigmentproperties, especially by good fastness to light and migration andweathering, and frequently by great brilliance of shade which issurprising for metal complexes and by high colour strength.

The following Examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated.

EXAMPLE 1

A mixture of 15.15 g (0.05 mole) of1-(cyano-carbanilidomethylene-3-hydrazinoisoindoline (prepared from1-(cyano-carbanilidomethylene)-3-imino-isoindoline and hydrazine) and9.45 g (0.05 mole) of 3-formyl-2,4-dihydroxyquinoline is stirred in 200ml of glacial acetic acid for 2 hours at 100° C. The reaction mixture isfiltered off hot. The filter residue is thoroughly washed with glacialacetic acid and ethanol and dried at 100° C. in vacuo. Yield: 21.5 g(90.7% of theory) of a yellowish orange pigment of the composition C₂₇H₁₈ N₆ O₃ and of the formula ##STR40## (only one of the possibleisomeric or tautomeric forms has been considered). The reaction of theresultant ligand with nickel acetate 0.4H₂ 0 (theory+10% surplus) in 600ml of methylcellosolve over the course of 3 hours at 110° C. leads to a1:1 Ni²⁺ complex which colours PVC and lacquers in orange red shades ofexcellent fastness to light, weathering and migration.

    ______________________________________                                        Microanalysis:                                                                          C.sub.27 H.sub.16 N.sub.6 NiO.sub.3 (MG 531)                                        C     H       N       Ni                                      ______________________________________                                                % estimated                                                                             61.05   3.04    15.82 11.05                                         % found   60.6    3.1     16.0  10.8                                  ______________________________________                                    

Instead of using methyl cellosolve, it is also possible to usecarbitols, glycols, dimethyl formamide or dimethyl sulphoxide for themetallising. If the metal complexes are not dried at a highertemperature than 100° C. in vacuo, they contain normally 0.5 to 2 molesof water of crystallisation.

The 1:1 metal complexes of the formula given below (only one of thepossible isomeric or tautomeric forms has been considered for the sakeof simplicity), in which M₁, A and X have the meanings indicated inTable 1, are synthesised according to the process of Example 1. Thestarting materials can be manufactured by known methods. ##STR41##

                  TABLE I                                                         ______________________________________                                         Example                                                                              M.sub.1.sup.2+                                                                         X                                                                                                   Shade in PVC                           ______________________________________                                        2      Ni.sup.2+                                                                              Cl                                                                                   ##STR42##      scarlet                                 3      Ni.sup.2+                                                                              H                                                                                    ##STR43##      scarlet                                 4      Ni.sup.2+                                                                              H                                                                                    ##STR44##      red                                     5      Ni.sup.2+                                                                              H                                                                                    ##STR45##      orange                                  6      Cu.sup.2+      "               yellowish                                                                     brown                                   ______________________________________                                    

EXAMPLE 7

A mixture of 15.15 g (0.05 mole) of1-(cyano-carbanilidomethylene)-3-hydrazinoisoindoline (prepared from1-(cyanocarbanilidomethylene)-3-imino-isoindoline and hydrazine) and9.45 g (0.05 mole) of 3-formyl-2,4-dihydroxyquinoline, to which is thenadded 13.75 g (0.055 mole) of nickel acetate. 4H₂ O, is stirred in 500ml of methyl cellosolve for 3 hours at 110° C. The reaction mixture isfiltered off hot. The filter residue is thoroughly washed with methylcellosolve and ethanol and dried at 80° C. in vacuo. Yield: 10.5 g(38.9% of theory) of an orange red nickel complex of the samecomposition (+0.5 mole of water of crystallisation) and pigmentproperties as in Example 1.

    ______________________________________                                        Microanalysis:                                                                          C.sub.27 H.sub.16 N.sub.6 NiO.sub.3 . 0,5 H.sub.2 O (MG 540)                        C     H       N       Ni                                      ______________________________________                                                % estimated                                                                             60.0    3.1     15.55 10.8                                          % found   59.8    3.2     15.3  10.8                                  ______________________________________                                    

Instead of using methyl cellosolve it is also possible to use carbitols,glycols, dimethyl formamide or dimethyl sulphoxide. If the metalcomplexes are not dried at a temperature higher than 100° C. in vacuothey normally still contain 0.5 to 2 moles of water of crystallisation.

The metal complexes of the formula given below (only one of the possibletautomeric or isomeric forms has been considered), in which M₁, Y, R₃and A have the meanings given in Table II, are synthesised according tothe single step process of Example 7. Some of the starting products areknown or can be manufactured by known methods. Column 6 indicates theratio of metal to ligand. ##STR46##

    __________________________________________________________________________     Example                                                                            M.sub.1.sup.2+                                                                    Y               R.sub.3                                                                                       M.sub.1 /L                                                                        Shade in PVC                    __________________________________________________________________________    8    Cu.sup.2+                                                                          ##STR47##      H                                                                                 ##STR48##   1/1 yellow- ish brown                9    Ni.sup.2+                                                                          ##STR49##      H  "            1/1 scarlet                          10   Ni.sup.2+                                                                          ##STR50##      H  "            1/2 yellow- ish orange               11   Ni.sup.2+                                                                          ##STR51##      H  "            1/1 orange                           12   Ni.sup.2+                                                                          ##STR52##      H  "            1/1 red                              13   Cu.sup.2+                                                                         "               H  "            1/1 brown                            14   Ni.sup.2+                                                                          ##STR53##      H  "            1/1 orange red                       15   Cu.sup.2+                                                                         "               H  "            1/1 brown                            16   Ni.sup.2+                                                                          ##STR54##      H  "            1/1 red                              17   Ni.sup.2+                                                                          ##STR55##      H                                                                                 ##STR56##   1/1 scarlet                          18   Ni.sup.2+                                                                          ##STR57##      H  "            1/2 red                              19   Ni.sup.2+                                                                          ##STR58##      H  "            1/1 orange                           20   Ni.sup.2+                                                                          ##STR59##      H  "            1/1 red                              21   Ni.sup.2+                                                                          ##STR60##      H  "            1/1 reddish brown                    22   Ni.sup.2+                                                                          ##STR61##      H                                                                                 ##STR62##   1/1 orange                           23   Cu.sup.2+                                                                         "               H  "            1/1 brown                            24   Ni.sup.2+                                                                          ##STR63##      H  "            1/1 yellowish orange                 25   Cu.sup.2+                                                                         "               H  "            1/1 yellowish                                                                     brown                            26   Ni.sup.2+                                                                          ##STR64##      H  "            1/1 red                              27   Ni.sup.2+                                                                          ##STR65##      H  "            1/1 orange                           28   Ni.sup.2+                                                                          ##STR66##      H  "            1/1 reddish  brown                   29   Ni.sup.2+                                                                          ##STR67##      H                                                                                 ##STR68##   1/1 scarlet                          30   Ni.sup.2+                                                                          ##STR69##      H  "            1/1 red                              31   Ni.sup.2+                                                                          ##STR70##      H  "            1/1 orange                           32   Ni.sup.2+                                                                         "               H                                                                                 ##STR71##   1/1 orange                           33   Ni.sup.2+                                                                          ##STR72##      H  "            1/1 orange                           34   Ni.sup.2+                                                                          ##STR73##      H  "            1/1 red                              35   Ni.sup.2+                                                                          ##STR74##      H                                                                                 ##STR75##   1/1 orange                           36   Ni.sup.2+                                                                          ##STR76##      H  "            1/1 orange                           37   Ni.sup.2+                                                                          ##STR77##      H  "            1/1 red                              38   Ni.sup.2+                                                                          ##STR78##      H                                                                                 ##STR79##   1/1 red                              39   Ni.sup.2+                                                                         "               H                                                                                 ##STR80##   1/1 red                              40   Ni.sup.2+                                                                         "               CH.sub.3                                                                          ##STR81##   1/1 red                              41   Cu.sup.2+                                                                         "               CH.sub.3                                                                         "            1/1 brown                            __________________________________________________________________________

EXAMPLE 42

A mixture of 14.4 g (0.05 mole) of1-(cyano-carbanilidomethylene)-3-imino-isoindoline and 10.15 g (0.05mole) of 3-formyl-2,4-dihydroxyquinoline-hydrazone (prepared by knownmethods) is stirred in 200 ml of glacial acetic acid for 1 hour at 95°C. The reaction mixture is filtered off hot. The filter residue isthoroughly washed with glacial acetic acid and ethanol and dried at 100°C. in vacuo. Yield: 21.3 g (89.8% of theory) of an orange pigment of thesame composition (C₂₇ H₁₈ N₆ O₃) as the ligand in Example 1, but ofother physical properties, such as UV, VIS, IR spectra and fragmentationin the mass spectrum. The reaction of the resultant ligand with nickelacetate. 4H₂ O (theory +10% surplus) in 600 ml of methyl cellosolve overthe course of three hours at 110° C. leads, as in Example 1, to a 1:1Ni²⁺ complex of the composition C₂₇ H₁₆ N₆ NiO₃, which colours PVC andlacquers in claret shades of good fastness to light and migration.

Instead of methyl cellosolve it is also possible to use carbitols,glycols, dimethyl formamide or dimethyl sulphoxide for the metallising.

If the metal complexes are not dried at a temperature higher than 100°C. in vacuo, they normally still contain 0.5 to 2 moles of water ofcrystallisation. The metal complexes of the formula given below (onlyone of the possible isomeric or tautomeric forms has been considered forthe sake of simplicity), in which M₁, Y, R₃ and A have tne meaningsgiven in Table III, are synthesised according to the process of Example42. Some of the starting materials are known or they can be manufacturedby known methods. Column 6 indicates the ratio of metal to ligand.##STR82##

                                      TABLE III                                   __________________________________________________________________________     ple Exam-                                                                         M.sub.1.sup.2+                                                                    Y                 R.sub.3                                                                                           M.sub.1 /L                                                                        Shade                      __________________________________________________________________________                                                      in PVC                      43  Ni.sup.2+                                                                          ##STR83##        H                                                                                 ##STR84##       1/1 brown                       44  Cu.sup.2+                                                                           "               H  "                1/1 brown                       45  Ni.sup.2+                                                                          ##STR85##        H  "                1/1 red                         46  Cu.sup.2+                                                                           "               H  "                1/1 brown                       47  Ni.sup.2+                                                                          ##STR86##        H  "                1/1 yellowish brown             48  Cu.sup.2+                                                                           "               H  "                1/1 brown                       49  Cu.sup.2+                                                                          ##STR87##        H  "                1/1 reddish brown               50  Ni.sup.2+                                                                          ##STR88##        H  "                1/1 claret                      51  Cu.sup.2+                                                                           "               H  "                1/1 claret                      52  Ni.sup.2+                                                                          ##STR89##        H  "                1/2 claret                      53  Cu.sup.2+                                                                           "               H  "                1/1 claret                      54  Ni.sup.2+                                                                          ##STR90##        H  "                1/1 claret                      55  Cu.sup.2+                                                                           "               H  "                1/1 violet                      56  Ni.sup.2+                                                                          ##STR91##        H  "                1/1 violet                      57  Ni.sup.2+                                                                          ##STR92##        H                                                                                 ##STR93##       1/1 claret                      58  Cu.sup.2+                                                                           "               H  "                1/1 red                         59  Ni.sup.2+                                                                          ##STR94##        H                                                                                 ##STR95##       1/1 yellowish   orange          60  Cu.sup.2+                                                                           "               H  "                1/1 brown                       61  Ni.sup.2+                                                                           "               H                                                                                 ##STR96##       1/1 red                         62  Cu.sup.2+                                                                           "               H  "                1/1 brown                       63  Ni.sup.2+                                                                           "               H                                                                                 ##STR97##       1/1 red                         64  Cu.sup.2+                                                                           "               H  "                1/1 brown                       65  Co.sup.2+                                                                           "               H  "                1/1 claret                      66  Ni.sup.2+                                                                          ##STR98##        H  "                1/1 reddish brown               67  Cu.sup.2+                                                                           "               H  "                1/1 brown                       68  Ni.sup.2+                                                                          ##STR99##        H  "                1/1 brown                       69  Cu.sup.2+                                                                            "              H  "                1/1 brown                       70  Cu.sup.2+                                                                          ##STR100##       H                                                                                 ##STR101##      1/1 brown                       71  Ni.sup.2+                                                                           "               H                                                                                 ##STR102##      1/1 claret                      72  Cu.sup.2+                                                                           "               H  "                1/1 brown                       73  Ni.sup.2+                                                                           "               CH.sub.3                                                                          ##STR103##      1/1 red                         74  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 brown                       75  Co.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 brown                       76  Ni.sup.2+                                                                          ##STR104##       CH.sub.3                                                                         "                1/1 red                         77  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 red                         78  Ni.sup.2+                                                                          ##STR105##       CH.sub.3                                                                         "                1/1 reddish brown               79  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 reddish                                                                       brown                       80  Ni.sup.2+                                                                          ##STR106##       CH.sub.3                                                                         "                1/2 reddish brown               81  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 brown                       82  Ni.sup.2+                                                                          ##STR107##       CH.sub.3                                                                          ##STR108##      1/1 claret                      83  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 violet                      84  Ni.sup.2+                                                                          ##STR109##       CH.sub.3                                                                         "                1/1 red                         85  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 violet                      86  Ni.sup.2+                                                                          ##STR110##       CH.sub.3                                                                         "                1/1 violet                      87  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 claret                      88  Ni.sup.2+                                                                          ##STR111##       CH.sub.3                                                                         "                1/2 yellow                      89  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/2 yellow                      90  Cu.sup.2+                                                                          ##STR112##       CH.sub.3                                                                         "                1/1 brown                       91  Ni.sup.2+                                                                          ##STR113##       CH.sub.3                                                                          ##STR114##      1/1 red                         92  Cu.sup.2+                                                                          ##STR115##       CH.sub.3                                                                         "                1/1 brown                       93  Ni.sup.2+                                                                          ##STR116##       CH.sub.3                                                                         "                1/1 red                         94  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 reddish                                                                       brown                       95  Ni.sup.2+                                                                          ##STR117##       CH.sub.3                                                                         "                1/1 claret                      96  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 red                         97  Ni.sup.2+                                                                          ##STR118##       CH.sub.3                                                                          ##STR119##      1/1 yellowish  orange           98  Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 yellow                      99  Ni.sup.2+                                                                          ##STR120##       CH.sub.3                                                                         "                1/1 red                         100 Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 red                         101 Ni.sup.2+                                                                          ##STR121##       CH.sub.3                                                                          ##STR122##      1/1 brown                       102 Cu.sup.2+                                                                           "               CH.sub.3                                                                         "                1/1 brown                       __________________________________________________________________________

EXAMPLES 103-107

The 1:1 copper (II) complexes of the formula given below, in which X₁and X₂ have the meanings given in the Table, are synthesised accordingto the process of Example 42. The starting materials are known or theycan be manufactured by known methods.

    ______________________________________                                         ##STR123##                                                                    Example                                                                              ##STR124##               PVCinShade                                   ______________________________________                                        103                                                                                   ##STR125##              yellowish brown                               104                                                                                   ##STR126##              brown                                         105                                                                                   ##STR127##              brown                                         106                                                                                   ##STR128##               reddish bronw                                107                                                                                   ##STR129##              yellowish brown                               ______________________________________                                    

EXAMPLE 108

A fine suspension of 6.62 g (0.02 mole) of the bishydrazone I (preparedby known methods from 3-formyl-2,4-dihydroxyquinoline, hydrazine and1,3-diimino-isoindoline) of the formula ##STR130## (only one of thepossible isomeric or tautomeric forms has been considered) and 2.56 g(0.02 mole) of barbituric acid in 200 ml of glacial acetic acid isprepared and stirred for 2 hours at 100° C. The reaction mixture isfiltered off hot. The filter residue is thoroughly washed with glacialacetic acid and ethanol and dried at 100° C. in vacuo. Yield: 7.15 g(80.8% of theory) of an orange pigment of the composition C₂₂ H₁₄ N₆ O₅and of the formula II ##STR131## (only one of the possible isomeric ortautomeric forms has been considered). The reaction of the resultantligand II with nickel acetate.4H₂ O (theory+10% surplus) in dimethylformamide over the course of 4 hours at 110° C. leads to a 1:1 Ni²⁺complex of the composition C₂₂ H₁₂ N₆ NiO₅ (% Ni est. 11.8; found 11.8).This pigment colours PVC and lacquers in red shades of excellentfastness to migration, light and weathering. The metallising can also beeffected simultaneously during the condensation of I with barbituricacid.

The 1:1 metal complexes of the formula given below (for simplicity'ssake only one of the possible isomeric or tautomeric forms has beenconsidered), in which M₁ and R₃ have the meanings indicated in Table IV,are synthesised according to the process of Example 108. The startingmaterials can be manufactured by known methods. ##STR132##

                  TABLE IV                                                        ______________________________________                                        Example    M.sub.1.sup.2+                                                                          R.sub.3  Shade in PVC                                    ______________________________________                                        109        Cu.sup.2+ H        brown                                           110        Ni.sup.2+ CH.sub.3 reddish brown                                   111        Cu.sup.2+ CH.sub.3 yellowish brown                                 ______________________________________                                    

EXAMPLE 112

1:1 Ni²⁺ complex of ##STR133##

For simplicity's sake only one of the possible isomeric or tautomericforms has been considered.

Manufacture of the Ligand

A mixture of 5.7 g (0.02 mole) of1-(cyano-benzimidazolylmethylene)-3-imino-isoindoline and 5.8 g (0.02mole) of 4,6-dichloro-3,5-dimethoxy-isoindolin-1-on-3-ylidene-hydrazineis heated in 250 ml of glacial acetic acid for 20 minutes to 80° C. Thered pigment is filtered off hot, washed with glacial acetic acid andalcohol and dried at 80° C. in vacuo. Yield: 8.7 g (78% of theory) of aproduct of the above formula which analysis shows to be pure.

Manufacture of the Ni²⁺ Complex

1.68 g (0.003 mole) of the bishydrazone are suspended in 50 ml of methylcellosolve and the suspension, together with 0.75 g (0.003 mole) ofnickel acetate.4H₂ O, is heated for 4 hours to 100° C. The redsuspension is filtered off hot and the filter product is thoroughlywashed with methyl cellosolve, alcohol and acetone and dried at 100° C.in vacuo. Yield: 1.55 g (84% of theory) of a pigment of the compositionC₂₇ H₁₅ Cl₂ N₇ NiO₃.

This pigment colours PVC and lacquers in brilliant red shades ofexcellent fastness to light and migration.

By analogous methods metal complexes are manufactured with the ligandsof the formula ##STR134## wherein M₁, Y, R₁ and R₂ have the meaningsgiven in Table II. Column 5 indicates the ratio of metal to ligand.

    __________________________________________________________________________     Exam- ple                                                                         M.sub.1.sup.2+                                                                    Y                                                                                             ##STR135##       M.sub.1 /L                                                                       Shade in PVC                     __________________________________________________________________________    113 Cu.sup.2+                                                                          ##STR136##                                                                                    ##STR137##      1/1 red                              114 Co.sup.2+                                                                           "             "                1/1 reddish                                                                       brown                            115 Ni.sup.2+                                                                          ##STR138##     "                1/1 reddish  brown                   116 Cu.sup.2+                                                                           "             "                1/1 brown                            117 Ni.sup.2+                                                                          ##STR139##                                                                                    ##STR140##      1/1 red                              118 Cu.sup.2+                                                                           "             "                1/1 red                              119 Co.sup.2+                                                                           "             "                1/1 claret                           120 Ni.sup.2+                                                                           "                                                                                            ##STR141##      1/1 reddish brown                    121 Cu.sup.2+                                                                           "             "                1/1 brown                            122 Co.sup.2+                                                                           "             "                1/1 brown                            123 Ni.sup.2+                                                                          ##STR142##                                                                                    ##STR143##      1/1 orange                           124 Cu.sup.2+                                                                           "             "                1/1 yellow                           125 Ni.sup.2+                                                                          ##STR144##     "                1/1 brown                            126 Cu.sup.2+                                                                           "             "                1/1 brown                            127 Ni.sup.2+                                                                          ##STR145##                                                                                    ##STR146##      1/2 red                              128 Cu.sup.2+                                                                           "             "                1/2 reddish                                                                       brown                            129 Ni.sup.2+                                                                          ##STR147##                                                                                    ##STR148##      1/1 red                              130 Cu.sup.2+                                                                           "             "                1/1 brown                            131 Ni.sup.2+                                                                          ##STR149##                                                                                    ##STR150##      1/1 red                              132 Cu.sup.2+                                                                           "             "                1/1 brown                            133 Ni.sup.2+                                                                           "                                                                                            ##STR151##      1/1 red                              134 Cu.sup.2+                                                                           "             "                1/1 red                              135 Ni.sup.2+                                                                           "                                                                                            ##STR152##      1/1 red                              136 Cu.sup.2+                                                                           "             "                1/1 reddish                                                                       brown                            137 Ni.sup.2+                                                                          ##STR153##                                                                                    ##STR154##      1/1 reddish brown                    138 Cu.sup.2+                                                                           "             "                1/1 brown                            139 Cu.sup.2+                                                                          ##STR155##                                                                                    ##STR156##      1/1 brown                            __________________________________________________________________________

EXAMPLE 140

A mixture of 5.7 g (0.02 mole) of1-(cyano-benzimidazolylmethylene)-3-iminoisoindoline, 5.8 g (0.02 mole)of 4,6-dichloro-3,5-dimethoxy-isoindolin-1-on-3-ylidene-hydrazine and5.0 g (0.02 mole) of nickel acetate.4H₂ O is heated in 250 ml of glacialacetic acid for 4 hours to 100° C. The red suspension is filtered offhot and the filter residue is thoroughly washed with glacial aceticacid, alcohol and acetone and dried in vacuo at 100° C. A pigment ofsimilar properties as in Example 112 is obtained.

EXAMPLE 141

5.7 g (0.02 mole) of1-(cyano-benzimidazolyl-methylene)-3-imino-isoindoline and 5.0 g (0.02mole) of nickel acetate.4H₂ O are reacted for 30 minutes at 50° C. in250 ml of glacial acetic acid. Then 5.8 g (0.02 mole) of4,6-dichloro-3,5-dimethoxyisoindolin-1-on-3-ylidene-hydrazine are addedand the suspension is heated for 4 hours to 100° C. The red suspensionis filtered off hot and the filter residue is thoroughly washed withglacial acetic acid, alcohol and acetone and dried in vacuo at 100° C. Apigment of similar properties as in Example 112 is obtained.

EXAMPLE 142

A mixture of 10 g of titanium dioxide and 2 g of the pigmentmanufactured according to Example 1 is ground for 48 hours in a ballmill with 88 g of a mixture of coconut alkyl resin, 24 g ofmelamine/formaldehyde resin (50% solids content), 8.8 g of ethyleneglycol monomethyl ether and 28.8 g of xylene.

By spraying this lacquer onto a aluminium sheet, predrying it for 30minutes at room temperature and then stoving it for 30 minutes at 120°C. there is obtained a scarlet finish which is characterised by verygood fastness to overstripe bleeding, light and weathering.

We claim:
 1. An azomethine metal complex of the formula ##STR157## inwhich R₃ is alkyl of 1 to 4 carbon atoms; M₁ is Ni, Cu, or Zn; R₆ ishydrogen, alkyl of 1 to 4 carbon atoms, phenyl, phenyl substituted byhalogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms;A is a radical of the formulae ##STR158## in which Q is methyl,alkoxycarbonyl with 2 to 5 carbon atoms or carbamoyl, R₈ is cyano, orcarbamoyl; R₉ is hydrogen, or hydroxy, Y₂ and Y₃ are hydrogen, halogen,alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or nitro,Y₄ is oxygen, sulfur or --NH--; Y₆ is hydrogen, carboxy, carbamoyl,alkoxycarbamoyl of 2 to 6 carbon atoms, alkylcarbamoyl of 2 to 6 carbonatoms, phenylcarbamoyl, phenylcarbamoyl substituted in the phenyl moietyby halogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbonatoms; Y₇ is hydrogen, halogen, methoxy, nitro or cyano.
 2. Anazomethine metal complex according to claim 1 of the formula ##STR159##wherein M₁ is Cu or Ni and R₃ is methyl.